Catalytic codimerization of norbornadiene with an acrylic acid ester

Abstract

Norbornadiene and an acrylic acid ester, e.g., methyl acrylate, are catalytically codimerized in the presence of a two-component homogeneous catalytic system consisting of nickel acetylacetonate and an alkyl aluminum chloride. The resulting codimer can be used as a precursor for a missile fuel. The ester portion of the acrylic acid ester is the radical RCH 2 O-- wherein the R is an H or an alkyl containing up to 10 carbon atoms.

It is claimed: 
     
       1. Process for the catalytic codimerization of norbornadiene with an acrylic acid ester comprising: (a) contacting norbornadiene and an acrylic acid ester, wherein the ester is RCH 2  O-- and R is an H or an alkyl containing one to ten carbon atoms, in the presence of a catalytic amount of a two-component homogeneous catalytic system consisting of nickel acetylacetonate and an alkyl aluminum chloride selected from the group consisting of diethylaluminum chloride, ethyl aluminum dichloride and ethyl aluminum sesquichloride:   (b) having the contacting occurring at a temperature within the range from between about -20° C. to about 100° C.; and   (c) continuing the contacting until a norbornadiene-acrylic acid ester codimer having the following structure ##STR4##  is prepared.   
     
     
       2. Process according to claim 1 wherein the alkyl aluminum chloride to the acetylacetonate mole ratio is in the range between from about 1 to about 100. 
     
     
       3. Process according to claim 1 wherein the norbornadiene to the ester mole ratio is in the range between from about 0.1 to about 20. 
     
     
       4. Process according to claim 1 wherein the norbornadiene to the acetylacetonate mole ratio is in the range between from about 10 to about 2000. 
     
     
       5. Process according to claim 4 wherein an inert solvent is present. 
     
     
       6. Process according to claim 5 wherein the inert solvent is selected from the group consisting of aromatic hydrocarbon, cycloparaffin, cycloolefin, ether, halogenated aromatic, halogenated paraffin and halogenated cycloparaffin. 
     
     
       7. Process according to claim 6 wherein the norbornadiene to the ester mole ratio is in the range between from about 0.1 to about 20. 
     
     
       8. Process according to claim 7 wherein the alkyl aluminum chloride to the acetylacetonate mole ratio is in the range between from about 1 to about 100. 
     
     
       9. Process according to claim 8 wherein the ester is methyl acrylate.